Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

• This invention pertains to polyolefin compositions stabilized with long chain N,N-dialkylhydroxylamines.
• US-A-4,590,231 describes the use of hydroxylamines including the N,N-di­alkylhydroxylamines as stabilizers for polyolefin compositions.
• the N,N-dialkylhydroxylamines are described generically as having alkyl of 1 to 18 carbon atoms and N,N-dioctylhydroxylamine is specifically disclosed as useful in such compositions. There is no mention of the longer chain N,N-dialkylhydroxylamines which are the subject of this invention.
• the stabilized polyolefin compositions described in this prior art patent also contain an alkaline metal salt of a fatty acid and a phenolic antioxidant.
• the compositions may optionally also contain a hindered amine light stabilizer or an organic phosphorus compound.
• US-A-3,408,422 describes the stabilization of unsaturated polyester compositions using various hydroxyl amines.
• US-A-4,242,224 describes the use of dialkylhydroxylamines to reduce or retard the pink discoloration found in amine antioxidant and antiozonant emulsions used in the rubber industry.
• US-A-4,316,996 pertains to the use of hydroxylamine compounds which can prevent the discoloration of phenolic antioxidants in rubber composi­tions.
• US-A-4,547,532 pertains to the use of hydroxylamines to prevent the premature increase in viscosity of polymer-based antifouling paints containing an organotin compound.
• US-A-4,409,408 discloses the use of N,N-dialkylhydroxylamines and tertiary alkylcatechols in stabilizing vinyl aromatic compounds, such as styrene, against premature polymerization.
• US-A-3,770,847 discloses hydroxylamines as curing catalysts for organo­polysiloxane compositions.
• the lower alkyl hydroxylamines are superior for this puprose.
• US-A-4,298,678 pertains to photosensitive compositions which contain substituted hydroxylamines.
• US-A-3,222,334 discloses N,N-dialkylhydroxylamines as short-stopping agents for emulsion polymerization and US-A-3,341,487 describes a process for stopping emulsion polymerization by the addition of dithiocarbamate salts and alkyl hydroxylamines.
• the instant invention pertains to stabilized compositions which comprise (a) a saturated polyolefin or mixture thereof, and (b) a long chain N,N-dialkylhydroxylamine of the formula I T1T2NOH (I) wherein T1 and T2 are independently alkyl of 12 to 18 carbon atoms.
• the polyolefin of the instant compositions is preferably a homopolymer or copolymer of an alpha-olefin.
• the saturated polyolefins useful in the instant compositions are the polymers derived from monoolefins, such as e.g. polyethylene, which can be crosslinked, polypropylene, polyisobutylene, polybutene-1, poly-3-­methylbutene-1 and poly-4-methylpentene-1.
• Polyethylene may be for example medium density, high density or linear low density polyethylene.
• Mixtures of the homopolymers cited above for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, or polypropylene and polyisobutylene and the like, may also be used.
• Copolymers of monoolefins may also be used in the instant compositions, for example ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/octene-1 copolymers, ethylene/butene-1 copolymers, ethylene/­octene-1 copolymers as well as ethylene/vinyl acetate copolymers.
• compositions particularly employ as the polyolefin component polyethylene, polypropylene, polyisobutylene, poly(butene-1), poly­(pentene-1), poly(3-methylbutene-1), poly(4-methylpentene-1) and various ethylene and propylene copolymers.
• Especially preferred polyolefin substrates are polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer, ethylene/propylene copolymer and copolymers of ethylene or of propylene with other alpha-olefins.
• the most preferred polyolefin substrate is polypropylene, high density polyethylene, ethylene/propylene copolymer or a copolymer of ethylene or of propylene with another alpha-olefin, low density polyethylene or linear low density polyethylene.
• the polyolefins used in the food wrapping industry are of particular interest in these compositions.
• Component (b) of the instant compositions is preferably a compound of the formula I wherein T1 and T2 are independently dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl. Most preferably T1 and T2 are the alkyl mixture found in hydrogenated tallow amine.
• Hydroxylamines of special interest are those compounds of formula I where T1 and T2 are each dodecyl, tetradecyl, hexadecyl or octadecyl; or where T1 is hexadecyl and T2 is tetradecyl, heptadecyl or octadecyl; or where T1 is heptadecyl and T2 is octadecyl.
• Hydroxylamines of the formula I wherein T1 and T2 are independently alkyl of 16 to 18 carbon atoms are also preferred.
• Hydroxylamines of special interest are also N,N-dioctadecylhydroxylamine and N,N-dihexadecylhydroxylamine or a mixture thereof.
• a typical di(hydrogenated tallow)amine has the following distribution of alkyl substituents: T1T2NH T1 T2 % C16 C14 1.9 C16 C16 12.4 C16 C17 2.8 C16 C18 36.0 C17 C18 3.9 C18 C18 39.0 other 4.0
• di(hydrogenated tallow)amine originating from animal sources may well vary somewhat in the specific distribution of alkyl substituents, but the di(hydrogenated tallow)amine contains major amounts of N,N-dihexadecylamine, N,N-dioctadecylamine and N-hexadecyl-N-octa­decylamine.
• the individual components of the mixture can be separated by distillation under high vacuum.
• the instant long chain N,N-dialkylhydroxylamines can be prepared by a number of methods. These include (A) the oxidation of the corresponding secondary amine with aqueous hydrogen peroxide to form the desired N,N-dialkylhydroxylamine directly; (B) the addition of the secondary amine to an alpha,beta-unsaturated compound such as an alkyl acrylate to form a Michael addition product, which is in turn oxidized to the corresponding tertiary amine oxide using aqueous hydrogen peroxide, and followed by the elimination of the alpha,beta-unsaturated compound by the Cope reaction to give the N,N-dialkylhydroxylamine; (C) the metathesis reaction between an alkyl halide and a hydroxylamine in the presence of alkali such as sodamide; and (D) the reaction of an amine with a peroxy compound, such as benzoyl peroxide, followed by saponification of the intermediate formed to the desired hydroxylamine derivative.
• the Food and Drug Administration requires that any stabilizers or additives used in food packaging resist being extracted or otherwise lost from the packaging material into the food it is supposed to protect.
• additives which are highly volatile or which can migrate easily or which are extracted by the food from the packaging material are unattractive however efficacious the additive may be as a stabilizer.
• Extraction studies are often carried out with heptane and with 50 % aqueous ethanol which simulate the kinds of food often used in packaged food.
• the instant long chain N,N-dialkylhydroxylamines are excellent process stabilizers for polyolefins when used alone in the absence of any phenolic antioxidant or even in the absence of any calcium stearate or other alkaline metal salt of a fatty acid.
• the hydroxylamine stabilizers of formula I are employed from about 0.01 to about 5 % by weight of the stabilized composition although this will vary with the particular substrate and application.
• An advan­tageous range is from about 0.025 to about 2 %, and especially 0.05 to about 1 %.
• the hydroxylamines of this invention stabilize polyolefins especially during high temperature processing with relatively little change in color and melt flow values even though the polymer may undergo a number of extrusions.
• the stabilized polyolefin compositions of the instant invention may also contain a stabilizer or mixture of stabilizers selected from the group consisting of the alkaline metal salts of fatty acids, the phenolic antioxidants, the hindered amine light stabilizers, the ultraviolet light absorbers, the organic phosphorus compounds and the thiosynergists.
• a stabilizer or mixture of stabilizers selected from the group consisting of the alkaline metal salts of fatty acids, the phenolic antioxidants, the hindered amine light stabilizers, the ultraviolet light absorbers, the organic phosphorus compounds and the thiosynergists.
• the instant long chain N,N-dialkyl­hydroxylamines are excellent process stabilizers for polyolefins when used in the presence of (c) an alkaline metal salt of a fatty acid or mixture thereof and in the absence of any other stabilizer.
• the alkaline metal salts of a fatty acid useful in the instant composi­tions are the alkali metal, alkaline earth metal, zinc, cadmium or aluminum salts of the higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, sodium ricinoleate or potassium palmitate. Calcium stearate or zinc stearate are particularly preferred.
• compositions may contain from 0.01 to 2 % of the alkaline metal salt of a fatty acid, preferably 0.05 to 1 %, and especially 0.1 to 0.5 % by weight of the stabilized composition.
• Another embodiment of the instant invention pertains to the instant compositions which additionally contain both (c) an alkaline metal salt of a fatty acid or mixture thereof, and (d) a phenolic antioxidant or mixture thereof.
• Still another embodiment of the instant invention pertains to the instant compositions which additionally contain (e) a hindered amine light stabilizer or mixture thereof.
• Another embodiment of the instant invention relates to the instant compositions which additionally contain (f) an organic phosphorus compound or mixture thereof.
• Still another embodiment of the instant invention involves the instant compositions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof, and (e) a hindered amine light stabilizer or mixture thereof.
• compositions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof, (d) a phenolic antioxidant or mixture thereof, and (e) a hindered amine light stabilizer or mixture thereof.
• Another embodiment of the instant invention involves the instant composi­tions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof, (d) a phenolic antioxidant or mixture thereof, and (f) an organic phosphorus compound or mixture thereof.
• compositions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof and (f) an organic phosphorus compound or mixture thereof.
• Still another embodiment of the instant invention involves the instant compositions which additionally contain (e) a hindered amine light stabilizer or mixture thereof, and (f) an organic phosphorus compound or mixture thereof.
• compositions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof, (e) a hindered amine light stabilizer or mixture thereof, and (f) an organic phosphorus compound or mixture thereof.
• Still another embodiment of the instant invention relates to the instant compositions which additionally contain (c) an alkaline metal salt of a fatty acid or mixture thereof, (d) a phenolic antioxidant or mixture thereof, (e) a hindered amine light stabilizer or mixture thereof, and (f) an organic phosphorus compound or mixture thereof.
• Another embodiment of the instant invention involves the instant composi­tions which additionally contain (d) a phenolic antioxidant or mixture thereof.
• the preferred long chain N,N-dialkylhydroxylamines of formula I used in these embodiments of the instant invention as well as the preferred alkaline metal salts of the fatty acids are described above.
• the pre­ferred phenolic antioxidants, hindered amine light stabilizers, ultra­violet light absorbers, organic phosphorus compounds and thiosynergists are set forth below.
• the phenolic antioxidants useful in the instant compositions embrace a large family of compounds examples of which are: Simple 2,6-dialkylphenols, such as, for example, 2,6-di-tert-butyl-4-­methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-­methoxymethylphenol, 2,6-dioctadecyl-4-methylphenol and 2,6-di-tert-­butylphenol.
• Simple 2,6-dialkylphenols such as, for example, 2,6-di-tert-butyl-4-­methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-­methoxymethylphenol, 2,6-dioctadecyl-4-methylphenol and 2,6-di-tert-­butylphenol.
• alkylated hydroquinones such as, for example, 2,5-di-­tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-di-tert-­butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-­butyl-4-hydroxyanisole, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-­4-hydroxyphenyl)adipate.
• alkylated hydroquinones such as, for example, 2,5-di-­tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-di-tert-­butyl-hydr
• Hydroxylated thiodiphenyl ethers such as, for example, 2,2′-thio-bis­(6-tert-butyl-4-methylphenol), 2,2′-thio-bis(4-octylphenol), 4,4′-thio-­bis(6-tert-butyl-3-methylphenol), 4,4′-thio-bis(3,6-di-sec-amylphenol), 4,4′-thio-bis(6-tert-butyl-2-methylphenol) and 4,4′-bis(2,6-dimethyl-­4-hydroxyphenyl)disulfide.
• 2,2′-thio-bis­(6-tert-butyl-4-methylphenol 2,2′-thio-bis(4-octylphenol), 4,4′-thio-­bis(6-tert-butyl-3-methylphenol), 4,4′-thio-bis(3,6-di-sec-amylphenol), 4,4′-thio-bis(6-
• Alkylidene-bisphenols such as, for example, 2,2′-methylene-bis(6-tert-­butyl-4-methylphenol), 2,2′-methylene-bis(6-tert-butyl-4-ethylphenol), 4,4′-methylene-bis(6-tert-butyl-2-methylphenol), 4,4′-methylene-bis(2,6-­di-tert-butylphenol), 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)4-­methylphenol, 2,2′-methylene-bis[4-methyl-6-(alpha-methylcyclohexyl)­ phenol], 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 1,1-bis(5-tert-­butyl-4-hydroxy-2-methylphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-­hydroxyphenyl)propane, 1,1,3-tris(5
• O-, N- and S-benzyl compounds such as, for example, 3,5,3′,5′-tetra-­tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-di­methylbenzyl-mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)­amine and bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephtha­late.
• Hydroxybenzylated malonates such as, for example, dioctadecyl 2,2-bis­(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-­butyl-4-hydroxy-5-methylbenzyl)malonate, bis(dodecylmercapto)ethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate and bis[4-(1,1,3,3-­tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)­malonate.
• dioctadecyl 2,2-bis­(3,5-di-tert-butyl-2-hydroxybenzyl)malonate dioctadecyl 2-(3-tert-­butyl-4-hydroxy-5-methylbenzyl)malonate
• Hydroxybenzyl-aromatic compounds such as, for example, 1,3,5-tris(3,5-­di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-­tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tris­(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• s-Triazine compounds such as, for example, 2,4-bis(octylmercapto)-6-­(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-4,6-­bis(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-­4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris­(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris(3,5-di-­tert-butyl-4-hydroxyphenylethyl)-s-triazine, 1,3,5-tris(2,6-dimethyl-­3-hydroxy-4-tert-butylbenzyl)isocyanurate and
• Amides of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as, for example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]­hexahydro-s-triazine and N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenyl­propionyl)hexamethylenediamine, N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxy­phenyl)propionyl]hydrazine.
• Esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, triethylene glycol, neopentylglycol, pentaerythritol, 3-thiaundecanol, 3-thiapenta­decanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris[hydroxyethyl]isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-­trioxabicyclo[2.2.2]octane.
• monohydric or polyhydric alcohols such as, for example, with
• Esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenol)propionic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thiaundecanol, 3-thiapenta­decanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris[hydroxyethyl]isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-­trioxabicyclo[2.2.2]octane.
• monohydric or polyhydric alcohols such as, for example, with methanol,
• Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-­propenediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane­diol, trimethylolethane, trimethylolpropane, tris[hydroxyethyl]iso­cyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]­octane, especially the tetrakis ester of pentaerythritol.
• Benzylphosphonates such as, for example, dimethyl 3,5-di-tert-butyl-4-­hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl­phosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl tert-butyl-4-hydroxy-3-methylbenzylphosphonate, and calcium bis(0-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate).
• the phenolic antioxidants of particular interest are n-octadecyl 3,5-di-­tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-­tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-­4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy­benzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy­hydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy­benzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-­hydroxyhydroc
• a most preferred phenolic antioxidant is neopentanetetrayl tetrakis­(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-­butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-­butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy­benzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol, 2,2′-ethylidene-bis­(4,6-di-tert-butylphenol) or calcium bis(0-ethyl 3,5-di-tert-butyl-4-­hydroxybenzylphosphonate).
• hindered amines may be for example 4-benzoyl-2,2,6,6-tetramethyl­piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-­tetramethylpiperidyl)sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-­triaza-spiro[4.5]decane-2,4-dione.
• the hindered amine light stabilizer of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)­sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, bis­(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxy­benzyl)butylmalonate, tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilo­triacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine
• a most preferred hindered amine light stabilizer is bis(2,2,6,6-tetra­methylpiperidin-4-yl)sebacate, the polycondensation product of 1-(2-­hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) or N,N′,N ⁇ ,N′′′-tetrakis[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)­amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane.
• such light absorbers may include the 2H-benzotriazoles, the benzophenones, the oxanilides, the alpha-cyanocinnamates, the substituted benzoate esters or the nickel salts of the O-alkyl hindered phenolic benzylphosphonates.
• UV light absorbers examples include 2-(2′-Hydroxyphenyl)benzotriazoles, e.g., the 5′-methyl-, 3′,5′-di-tert-­butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-­di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-­butyl-, 3′-alpha-methyl-benzyl-5′-methyl-, 3′-alpha-methyl-benzyl-5′-­methyl-5-chloro-, 4′-hydroxy-, 4′-methoxy-, 4′-octyloxy-, 3′,5′-di-tert-­amyl-, 3′-methyl-5′-carbomethoxyethyl- and 5-
• 2,4-Bis(2′-hydroxyphenyl)-6-alkyl-s-triazines e.g., the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.
• 2-Hydroxybenzophenones e.g., the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2′,4′-trihydroxy-, 2,2′,4,4′-tetrahydroxy- or 2′-hydroxy-4,4′-dimethoxy-derivative.
• 1,3-Bis(2′-hydroxybenzoyl)benzenes e.g., 1,3-bis(2′-hydroxy-4′-hexyl­oxybenzoyl)benzene, 1,3-bis(2′-hydroxy-4′-octyloxybenzoyl)benzene or 1,3-bis(2′-hydroxy-4′-dodecyloxybenzoyl)benzene.
• Esters of optionally substituted benzoic acids e.g., phenyl salicylate, octylphenyl salicylate, dibenzoylresorcin, bis(4-tert-butylbenzoyl)­resorcin, benzoylresorcin, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester or 2-octadecyl ester or 2-methyl-4,6-di-­tert-butyl ester.
• benzoic acids e.g., phenyl salicylate, octylphenyl salicylate, dibenzoylresorcin, bis(4-tert-butylbenzoyl)­resorcin, benzoylresorcin, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl
• Acrylates e.g., alpha-cyano- ⁇ , ⁇ -diphenylacrylic acid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-­cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or butyl ester or N-( ⁇ -carbomethoxyvinyl)-2-methyl-indoline.
• Oxalic acid diamides e.g., 4,4′-dioctyloxy-oxanilide, 2,2′-dioctyloxy-­5,5′-di-tert-butyloxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butyl­oxanilide, 2-ethoxy-2′-ethyl-oxanilide, N,N′-bis(3-dimethylaminopropyl)­oxalamide, 2-ethoxy-5-tert-butyl-2′-ethyloxanilide and the mixture thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butyl-oxanilide, or mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
• the ultraviolet light absorber useful in the instant composi­tions is 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-­3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis­(alpha,alpha-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-5-­tert-octylphenyl)-2H-benzotriazole, 2-hydroxy-4-octyloxy-benzophenone, nickel bis(0-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), 2,4-dihydroxybenzophenone, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-­2H-benzotriazole, nickel butylamine complex with 2,2′-thiobis(4-tert-­butylphenol), 2-ethoxy-2′-ethoxy-2
• compositions contain an organic phosphorus compound
• organic phosphorus compound such compounds may be, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-bis(isodecyloxy)-­2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane and tris(4-hydroxy-3,5-­di-tert-butylphenyl)phosphite or similar phosphonites.
• the organic phosphorus compound of particular interest is selected from the group consisting of tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis­(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane, tris(p-nonylphenyl)phosphite, 3,9-bis(2,6-di-tert-butyl-4-methyl­phenoxy)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane, 3,9-distearyloxy-­2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane, dilauryl phosphite, 3,9-bis[2,6-di-tert-butyl-4-(2-(n-octadecyloxycarbonyl)ethyl)phenoxy]
• thiosyner­gists may be for example dilauryl thiodipropionate, distearyl thiodi­propionate or neopentanetetrayl tetrakis(3-dodecylthiopropionate).
• Distearyl thiodipropionate or dilauryl thiodipropionate is particularly preferred.
• Metal deactivators e.g., oxanilide, isophthalic acid dihydrazide, sebacic acid bis[phenylhydrazide], bis-benzylidene-oxalic acid hydrazide, N,N′-diacetal adipic acid dihydrazide, N,N′-bis(salicyloyl)oxalic acid dihydrazide, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-­4-hydroxyphenylpropionyl)hydrazine, N-salicyloyl-N′-salicylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N′-bis(salicyloyl)thiopropionic acid dihydrazi
• Metal deactivators e.g., oxanilide, iso
• Nucleation agents e.g., 4-tert-butylbenzoic acid, adipic acid, diphenyl­acetic acid or substituted sorbitols such as 1,3,2,4-dibenzylidene-­sorbitol.
• additives that can be incorporated in the stabilized compositions are antiblocking agents, clarifiers, antiozonants, lubricants such as e.g. stearyl alcohol, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, colorants, dyes, optical brighteners, flame-­proofing agents and antistatic agents.
• antiblocking agents e.g. stearyl alcohol, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, colorants, dyes, optical brighteners, flame-­proofing agents and antistatic agents.
• the stabilizers may be readily incorporated into the polyolefins by conventional techniques at any convenient stage prior to the manufacture of shaped articles therefrom.
• the stabilizers may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer.
• the stabilized polyolefin compositions contain conventional additives such as the materials listed above, e.g. phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds and thiosynergists, these additives may be present in a concentration of e.g. about 0.01 to about 5 %, preferably about 0.025 to about 2 %, and especially about 0.1 to about 1 %, by weight of the stabilized composition.
• additives such as the materials listed above, e.g. phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds and thiosynergists
• these additives may be present in a concentration of e.g. about 0.01 to about 5 %, preferably about 0.025 to about 2 %, and especially about 0.1 to about 1 %, by weight of the stabilized composition.
• This oil (5.0 g) is purified by column chromatography using hexane and ethyl acetate solvents on silica gel to give 4.9 g (98 % recovery) of a colorless oil. Analysis: Calcd for C28H57NO2: C, 76.5; H, 13.1; N, 3.2. Found: C, 76.6; H, 13.0; N, 3.1.
• This oil (5.0 g) is purified by column chromatography using hexane and ethyl acetate solvents on silica gel to give 4.9 g of a colorless oil. Analysis: Calcd for C32H65NO2: C, 77.5; H, 13.2; N, 2.8. Found: C, 77.8; H, 13.4; N, 3.0.
• Example 2 Using the general procedure of Example 2, 57.5 g (0.116 mol) of the product of Example 7 in 450 ml of isopropanol is oxidized using 5.6 ml (0.15 mol) of 70 % aqueous hydrogen peroxide solution to give 21.5 g (44 % yield) of the above-named product as a white solid melting at 94-96°C. Analysis: Calcd for C28H59NO: C, 79.0; H, 14.0; N, 3.3. Found: C, 79.2; H, 14.0; N; 3.2.
• the above-named product is isolated from the reaction mixture by filtra­tion.
• the filter cake is washed with two 50 ml portions of n-butanol at 55°C; then dried to give the desired product in a yield of 63 g (68 %) as a white solid melting at 93-96°C.
• TLC thin layer chromatography
• the above-named product is isolated from the reaction mixture by filtra­tion.
• the filter cake is washed with 100 ml of n-butanol at 55°C, and then with two 200 ml portions of methanol at ambient temperature to give the desired product in a yield of 27.6 g (57 %) as a white solid melting at 98-100°C.
• Example 11 The general procedure of Example 11 is followed using 100 g (0.19 mol) of dihexadecylamine (451 eq. wt., 88 % secondary amine, 30.2 g (0.44 mol) of 50 % aqueous hydrogen peroxide solution and 400 ml of ethanol. After stirring for 48 hours, the reaction mixture is filtered to give the above-named product which is twice recrystallized from 500 ml of chloro­form. The desired product is obtained in a yield of 29.4 g (32 %) as white needles melting at 97-99°C. Analysis: Calcd for C32H67NO: C, 79.8; H, 14.0; N, 2.0. Found: C, 79.5; H, 14.0; N, 2.7.
• Example 12 The general procedure of Example 12 is followed using at 50 to 55°C 50 g (0.12 mol) of ditetradecylamine, 200 ml of n-propanol and 8.3 g (0.12 mol) of 50 % aqueous hydrogen peroxide solution.
• the above-named product is obtained in a yield of 33.4 (64 %) as white needles melting at 97-99°C.
• Example 16 Process Stabilization of polypropylene at 260°C
• the base formulation comprises 100 parts of unstabilized polypropylene (®Profax 6501, Himont) with 0.10 parts of calcium stearate. N,N-Di­(hydrogenated tallow)hydroxylamine is solvent blended onto the propylene from a solution in methylene chloride. After removal of the solvent by evaporation under reduced pressure, the stabilized resin formulation is extruded at 100 rpm from a 2.54 cm diameter extruder at 260°C.
• resin pellets are compression molded into 3.2 mm thick plaques at 193°C and specimen yellowness index (YI) is determined according to ASTM D-1925. Low YI values indicate less yellowing. Additionally, the melt flow rate (in g/10 minutes) according to ASTM D-1238 is measured on the pellets after the first and fifth extrusions. The closer the melt flow rate after the fifth extrusion is to the melt flow rate after the first extrusion indicates superior process stabilization of the polypropylene.
• Example 17 Process Stabilization of Polypropylene at 288°C
• polypropylene (®Spheripol 6301, Himont) containing 0.1 % by weight of calcium stearate is extruded at 288°C with N,N-di(hydrogenated tallow)hydroxylamine.
• the yellowness index values and melt flow rate values are determined as described in Example 16 to ascertain the efficacy of each stabilizer in protecting the polymer during this high temperature processing.
• Example 18 Process Stabilization of Polypropylene at 260°C
• polypropylene (®Profax 6301, Himont) containing 0.1 % by weight of calcium stearate plus various hydroxylamines is converted into pellets by extrusion at 260°C and separately spun at 260°C into filament (10-11 dtex) form. The melt flow rate is determined for the pellets and for the corresponding fibers. Hydroxylamine Hydroxylamine Concentration % by wt.
• HA 4 is N,N-didodecylhydroxylamine.
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• HA 6 is N-N-ditetradecylhydroxylamine.
• HA 7 is N,N-di(hydrogenated tallow)hydroxylamine containing a large amount of hexadecyl, heptadecyl and octadecyl components.
• Example 19 Process Stabilization of Polypropylene at 260°C
• Example 16 Following the general procedure of Example 16, another polypropylene (®El Paso PP) containing 0.1 % of zinc stearate is stabilized with N,N-di(hydrogenated tallow)hydroxylamine.
• the effectiveness of the hydroxylamine is measured by the determination of melt flow rate values on the test samples after extrusions at 260°C. % by weight of N,N-Di(hydrogenated tallow)hydroxylamine Melt Flow Rate After Extrusion 1 5 - 5.9 10.0 0.05 3.4 5.0 0.1 3.5 4.7
• Propylene (®Profax 6501, Himont) containing 0.1 % by weight of calcium stearate, 0.033 % by weight of neopentanetetrayl tetrakis(3,5-di-tert-­butyl-4-hydroxyhydrocinnamate), 0.067 % by weight of tris(2,4-di-tert-­butylphenyl) phosphite and 0.25 % by weight of a N,N-dialkylhydroxylamine test compound is extruded at 260°C. The extruded composition is then compression molded at 227°C into a plaque having the dimensions of 2.54 cm x 5.08 cm x 0.77 mm and containing 1 g of polypropylene.
• test plaques are extracted with 50 ml of 50 % aqueous ethanol at 49°C for 10 days after being exposed for an initial period of 2 hours in said solvent at 66°C. These extraction conditions conform to those required by the FDA in assessing the acceptability of additives for use in food packaging.
• the concentration of the test additive in the plaques is determined using chemiluminescence based on nitrogen content.
• the sample plaques are analyzed by combusting a 200 mg sample in the furnace of an Antek chemiluminescence nitrogen analyzer with a programmed combustion from 120°C to 700°C.
• the plaques are analyzed before and then after extraction with the 50 % aqueous ethanol.
• a polypropylene plaque containing no nitrogen containing hydroxylamine additive is used as a blank. Analyses are done in quadruplicate with the average values reported in the table below.
• HA 4 is N,N-didodecylhydroxylamine.
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• HA 6 is N,N-ditetradecylhydroxylamine.
• HA 7 is N,N-di(hydrogenated tallow)hydroxylamine containing a large amount of hexadecyl, heptadecyl and octadecyl components.
• Example 21 Process Stabilization of Polypropylene at 260°C
• YI Yellowness index
• MFR melt flow rate
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• the fibers are exposed in a Xenotest 1200 (Fa. Heraeus) xenon arc weatherometer.
• the exposure time needed for the initial tensile strength of the fiber tow to fall to half it original value is the criterion used to assess failure in this test.
• Stabilizer Time in Xenotest 1200 till initial tensile strength falls in half 0.2 % by wt. of HALS A plus 1630 0.1 % by wt. of HA 5 0.2 % by wt. of HALS A plus 1850 0.1 % by wt. of AO N plus 0.1 % by wt. of HA 5 HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• HALS A is the polycondensation product of 2,4-dichloro-6-tert-octyl-amino-s-triazine and 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine).
• AO N is calcium bis(O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) mixed with wax in a 1:1 ratio.
• the stabilized composition always contains 0.1 % by weight of calcium stearate.
• the polypropylene compounded as described in Example 22 is molded at 230°C for 3 minutes to give plaques of 1 mm thickness. From these plaques strips (10 mm x 130 mm) are cut which are aged in an air circulating oven at 120°C. The test specimens are considered to have failed (embrittled) when they break when bended with a bending radius of 5 mm. The time in days to reach this embrittlement is recorded in the table below. Stabilizer Days at 120°C till Embrittlement 0.1 % by wt. of HA 5 plus 16 0.1 % by wt.
• AO N HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• AO N is calcium bis(O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) mixed with wax in a 1:1 ratio.
• fiber grade polypropylene containing 0.1 % by weight of calcium stearate and 0.011 % of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate is compounded with the various test stabilizers.
• a portion of the compounded polymer is directly molded at 230°C for 3 minutes to give plaques of 1 mm thickness.
• Another portion of the compounded polymer is first spun at 270°C into fibers. The fibers are then converted into plaques of 1 mm thickness. From these plaques, specimen strips are cut which are aged in an air circulating oven at 149°C.
• test specimens are considered to be brittle when they break when bended with a radius of 5 mm.
• the time in days to reach this embrittlement is recorded in the table below.
• Stabilizer Days to Embrittlement on Oven Aging at 149°C Molded Directly into Plaques Spun First then Molded into Plaque 0.1 % by wt. of HALS A plus 11 7 0.1 % by wt. of HA 5 0.05 % by wt. of HALS A plus 7 3 0.1 % by wt. of HA 5 HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• HALS A is the polycondensation product of 2,4-dichloro-6-tert-octyl-amino-s-triazine and 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine).
• the combination of hindered amine stabilizer with an instant hydroxylamine greatly enhances the time till failure (embrittlement) occurs.
• the enhancement is particularly observed when the polypropylene composition is subjected to severe shear forces at high temperature as they occur in fiber spinning and injection molding.
• Example 25 Process Stabilization of Polypropylene at 260°C
• HA 5 AO F is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• polypropylene (®Profax 6501, Himont) containing 0.1 % by weight of calcium stearate and 0.05 % by weight of neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-­hydroxyhydrocinnamate) and the additional test additives indicated in the table below is extruded into pellets. The pellets are pressed at 240°C for 6 minutes to prepare the 1 mm test plaques.
• test plaques are then examined for color by the Yellowness Index (YI) method (ASTM D 1925) before aging or exposure to hot water. Separate plaques are exposed to oven aging for 21 days at 120°C or at 135°C; or to exposure in water at 90°C for 7, 14, 21, 28 or 35 days. Yellowness index values are obtained on each plaque after said exposure. The YI values are recorded in the table below. Low YI values indicate less yellowing or discoloration. Run A B C D Extrusion Temp. °C 280 280 260 260 % by wt. of tris(2,4-di-tert-butylphenyl)phosphite 0.05 0.025 - - % by wt.
• YI Yellowness Index
• polypropylene (®Propathene HF 26, ICI) containing 0.1 % by weight of calcium stearate and containing various test additives indicated in the table below is extruded at 260°C. Melt flow rates and yellowness index values are measured after the 1st, 3rd and 5th extrusions to ascertain the effec­tiveness of the stabilizers present. Stabilizer Yellowness Index Color After Extrusion Melt Flow Rate After Extrusion 1 3 5 1 3 5 0.075 % by wt. of HA 5 plus 4.1 5.4 7.1 2.6 2.2 2.8 0.0375 % by wt. of AO F plus 0.0375 % by wt.
• Phosphorus I 0.075 % by wt. of HA 5 plus 3.8 5.2 7.8 2.0 2.5 2.6 0.025 % by wt. of AO F plus 0.05 % by wt. of Phosphorus I
• AO F is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
• Phosphorus I is tris(2,4-di-tert-butylphenyl) phosphite.
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• polypropylene (®Spheripol, Himont) containing 0.1 % by weight of calcium stearate and the additional stabilizers listed in the table below is extruded at 260°C or at 280°C.
• the melt flow rate and yellowness index values are measured after the 1st, 3rd and 5th extrusions to assess the efficacy of the stabilizers present in the test sample.
• Extrusion at 260°C Stabilizer Yellowness Index Color After Extrusion Melt Flow Rate After Extrusion 1 3 5 1 3 5 0.05 % by wt. of AO L plus 4.3 5.2 7.3 3.2 3.7 4.3 0.1 % by wt. of HALS A plus 0.1 % by wt.
• HALS A is the polycondensation product of 2,4-dichloro-6-tert-octyl-amino-s-triazine and 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine).
• HA 5 is N,N-di(hydrogenated tallow)hydroxylamine.
• polypropylene (®Propathene HF 26, ICI) containing 0.1 % by weight of calcium stearate and the additional stabilizers listed in the table below is extruded at 300°C.
• the melt flow rate and yellowness index values are measured after the 1st, 3rd and 5th extrusions to assess the efficacy of the stabilizers present in the test sample.
• a mixture of phenolic antioxidant and hydroxylamine, which may optionally contain a phosphorus compound is very effective in stabilizing the melt flow rate value without perceptible discoloration.
• Stabilizer Yellowness Index Color After Extrusion Melt Flow Rate After Extrusion 1 3 5 1 3 5 0.05 % by wt. of AO F plus 5.9 12.9 21.1 3.7 4.0 4.5 0.1 % by wt. of HA 5 0.05 % by wt. of AO F plus 5.1 8.8 17.1 2.6 3.4 3.6 0.075 % by wt. of HA 5 plus 0.025 % by wt. of Phosphorus I 0.05 % by wt.
• AO F is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
• Phosphorus I is tris(2,4-di-tert-butylphenyl)phosphite.
• HA 5 is di(hydrogenated tallow)hydroxylamine.

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